超声辅助熔融草酸法高效绿色再生饱和活性炭

doi:10.16085/j.issn.1000-6613.2021-0667

摘要/Abstract

摘要：

饱和活性炭的高效绿色再生对活性炭在污染物吸附过程中的循环利用是非常重要的。本文利用超声波辅助熔融草酸的方法对饱和活性炭进行高效绿色再生，讨论了温度、时间、超声振幅和固液比对饱和活性炭再生效率的影响。结果表明，在超声辅助作用下，熔融草酸可在20min内使饱和活性炭得到快速再生，再生效率高达94.72%。通过5次吸附-脱附循环后，再生效率仍可达到78.02%，与此同时有机酸的回收率极高，平均达到98.35%，再生过程十分绿色环保。在超声的辅助作用下，强氢键缔合能力的熔融草酸更充分地与焦糖反应，形成草酸-焦糖强氢键缔合体系，降低焦糖与活性炭表面的亲和力，将焦糖解吸，实现活性炭的再生。该法可为绿色高效的活性炭再生方法的研究开发提供新思路。

关键词: 活性炭, 再生, 超声辅助, 固体有机酸

Abstract:

The effective green regeneration of saturated activated carbon is very important for the recycling of activated carbon in the process of pollutant adsorption. In this paper, the method of ultrasonic assisted melting oxalic acid was used to regenerate the saturated activated carbon with high efficiency and green. The effects of temperature, time, ultrasonic amplitude and solid-liquid ratio on the regeneration efficiency of saturated activated carbon were discussed. The results showed that the saturated activated carbon can be regenerated rapidly in 20 minutes by molten oxalic acid under the assistance of ultrasound and the regeneration efficiency was as high as 94.72%. After five adsorption desorption cycles, the regeneration efficiency can still reach 78.02% and the recovery rate of organic acids was very high with an average of 98.35%, and thus green regeneration was realized. Under the assistance of ultrasound, the molten oxalic acid with strong hydrogen bond association ability reacted more fully with caramel to form a strong hydrogen bond association system between oxalic acid and caramel, which reduced the affinity between caramel and activated carbon surface. Then, the adsorbate can be desorbed to achieve the regeneration of the activated carbon. This method can provide a new idea for the research and development of green and efficient activated carbon regeneration method.

Key words: activated carbon, regeneration, ultrasound-assisted, solid organic acid

中图分类号:

蔡政汉, 何晨露, 谢海亮, 王琼, 陈燕丹, 吕建华, 郑新宇, 黄彪, 林冠烽. 超声辅助熔融草酸法高效绿色再生饱和活性炭[J]. 化工进展, 2022, 41(4): 2115-2122.

CAI Zhenghan, HE Chenlu, XIE Hailiang, WANG Qiong, CHEN Yandan, LYU Jianhua, ZHENG Xinyu, HUANG Biao, LIN Guanfeng. Method of ultrasonic assisted melting oxalic acid for effective green regeneration of saturated activated carbon[J]. Chemical Industry and Engineering Progress, 2022, 41(4): 2115-2122.

图/表 9

图1 超声辅助草酸再生饱和活性炭以及草酸回收流程图

图2 各主要影响因素对再生效率的影响

图3 r-AC、AC、s-AC、滤液、草酸和焦糖的FTIR谱图

图4 AC、s-AC和r-AC的N2吸附-脱附等温线和孔径分布

表1 AC、s-AC和r-AC的孔隙结构参数

材料

比表面积

/m²·g^-1

总孔容积

/cm³·g^-1

微孔孔容

/cm³·g^-1

中孔孔容

/cm³·g^-1

平均孔径

/nm

图5 焦糖和滤液的凝胶渗透色谱谱图

图6 AC、s-AC和r-AC的热重曲线及DTG曲线

图7 超声辅助熔融草酸对饱和活性炭的再生机理示意图

图8 不同吸附-脱附循环次数的再生效率和草酸回收率

参考文献 35

1	KOSAKA K, IWATANI A, TAKEICHI Y, et al. Removal of haloacetamides and their precursors at water purification plants applying ozone/biological activated carbon treatment[J]. Chemosphere, 2018, 198: 68-74.
2	KANE A, GIRAUDET S, VILMAIN J B, et al. Intensification of the temperature-swing adsorption process with a heat pump for the recovery of dichloromethane[J]. Journal of Environmental Chemical Engineering, 2015, 3(2): 734-743.
3	蔡炳良. 活性炭吸附-热氮脱附-超重力精馏回收有机溶剂[J]. 中国环保产业, 2018(3): 51-53.
	CAI Bingliang. Organic solvents reclaimed by activated carbon adsorption-thermal nitrogen desorption-ultra-gravity rectification[J]. China Environmental Protection Industry, 2018(3): 51-53.
4	KOW S H, FAHMI M R, ABIDIN C Z A, et al. Regeneration of spent activated carbon from industrial application by NaOH solution and hot water[J]. Desalination and Water Treatment, 2016, 57(60): 29137-29142.
5	NEWSWIRE P. Global and China activated carbon industry report, 2018—2023[J]. .
6	NATH K, BHAKHAR M S. Microbial regeneration of spent activated carbon dispersed with organic contaminants: mechanism, efficiency, and kinetic models[J]. Environmental Science and Pollution Research, 2011, 18(4): 534-546.
7	刘小艳, 蔡万欣, 赵立坤, 等. 活性炭去除游离氯的失效机制及热再生研究[J]. 化工学报, 2020, 71(4): 1781-1790.
	LIU Xiaoyan, CAI Wanxin, ZHAO Likun, et al. Failure mechanism and regeneration of activated carbon for free chlorine removal[J]. CIESC Journal, 2020, 71(4): 1781-1790.
8	高志鹏, 刘成, 陶辉, 等. 生物活性炭的热再生效能及在水厂中的应用[J]. 中国给水排水, 2019, 35(15): 48-53
	GAO Zhipeng, LIU Cheng, TAO Hui, et al. Thermal regeneration effect of biological activated carbon and its application in waterworks[J]. China Water & Wastewater, 2019, 35(15): 48-53.
9	李碟, 卢钧, 刘晓琛, 等. 饱和粉末活性炭电化学再生研究[J]. 环境污染与防治, 2020, 42(4): 417-421, 425.
	LI Die, LU Jun, LIU Xiaochen, et al. Study on electrochemical regeneration of saturated powdered activated carbon[J]. Environmental Pollution & Control, 2020, 42(4): 417-421, 425.
10	汪南方, 华坚, 尹华强, 等. 微波加热活性炭的制备、再生和改性[J]. 化工进展, 2004, 23(6): 624-628.
	WANG Nanfang, HUA Jian, YIN Huaqiang, et al. Application of microwave heating in preparing, regenarating and modifying activated carbons[J]. Chemical Industry and Engineering Progress, 2004, 23(6): 624-628.
11	DURÁN-JIMÉNEZ G, STEVENS L A, HODGINS G R, et al. Fast regeneration of activated carbons saturated with textile dyes: textural, thermal and dielectric characterization[J]. Chemical Engineering Journal, 2019, 378: 121774.
12	卢炯元. 双频超声波协同再生吸附苯酚饱和活性炭研究[D]. 兰州: 兰州交通大学, 2019.
	LU Jiongyuan. Study on adsorption of phenol saturated activated carbon by dual-frequency ultrasound[D]. Lanzhou: Lanzhou Jiaotong University, 2019.
13	唐晓东, 陆海, 李晶晶, 等. 低温一步法活性炭基脱硫剂的制备与评价[J]. 燃料化学学报, 2018, 46(5): 633-640.
	TANG Xiaodong, LU Hai, LI Jingjing, et al. Preparation and evaluation of activated carbon-based desulfurization adsorbent by one-step method at low temperature[J]. Journal of Fuel Chemistry and Technology, 2018, 46(5): 633-640.
14	MIGUET M, GOETZ V, PLANTARD G, et al. Sustainable thermal regeneration of spent activated carbons by solar energy: application to water treatment[J]. Industrial & Engineering Chemistry Research, 2016, 55(25): 7003-7011.
15	MIGUEL G SAN, LAMBERT S D, GRAHAM N J D. The regeneration of field-spent granular-activated carbons[J]. Water Research, 2001, 35(11): 2740-2748.
16	CHEN J, QIN Y F, CHEN Z H, et al. Gas circulating fluidized beds photocatalytic regeneration of I-TiO₂ modified activated carbons saturated with toluene[J]. Chemical Engineering Journal, 2016, 293: 281-290.
17	WEDEKING C A, SNOEYINK V L, LARSON R A, et al. Wet air regeneration of PAC: comparison of carbons with different surface oxygen characteristics[J]. Water Research, 1987, 21(8): 929-937.
18	林冠烽, 牟大庆, 程捷, 等. 活性炭再生技术研究进展[J]. 林业科学, 2008, 44(2): 150-154.
	LIN Guanfeng, MU Daqing, CHENG Jie, et al. Research progress on regeneration of active carbon[J]. Scientia Silvae Sinicae, 2008, 44(2): 150-154.
19	YAO Y. Enhancement of mass transfer by ultrasound: application to adsorbent regeneration and food drying/dehydration[J]. Ultrasonics Sonochemistry, 2016, 31: 512-531.
20	YAO Y, WANG W, YANG K. Mechanism study on the enhancement of silica gel regeneration by power ultrasound with field synergy principle and mass diffusion theory[J]. International Journal of Heat and Mass Transfer, 2015, 90: 769-780.
21	YANG K, YAO Y, LIU S, et al. Separation of ultrasonic contributions and energy utilization characteristics of ultrasonic regeneration[J]. AIChE Journal, 2014, 60(5): 1843-1853.
22	LIU C, SUN Y, WANG D, et al. Performance and mechanism of low-frequency ultrasound to regenerate the biological activated carbon[J]. Ultrasonics Sonochemistry, 2017, 34: 142-153.
23	SUN Z H, LIU C, CAO Z, et al. Study on regeneration effect and mechanism of high-frequency ultrasound on biological activated carbon[J]. Ultrasonics Sonochemistry, 2018, 44: 86-96.
24	JING G H, ZHOU Z M, SONG L, et al. Ultrasound enhanced adsorption and desorption of chromium (VI) on activated carbon and polymeric resin[J]. Desalination, 2011, 279(1/2/3): 423-427.
25	WANG Y H, YANG R T. Desulfurization of liquid fuels by adsorption on carbon-based sorbents and ultrasound-assisted sorbent regeneration[J]. Langmuir, 2007, 23(7): 3825-3831.
26	LYU G, WU L, WANG X, et al. Regeneration of caramel saturated activated carbon jointly by microwave and extractive method[J]. International Journal of Chemical Reactor Engineering, 2012, 10(1). DOI:10.1515/1542-6580.3117 .
27	张成旺, 左宋林, 胡贺. 废弃粉状活性炭制备糖液脱色用成型活性炭[J]. 林业工程学报, 2016, 1(4): 69-73.
	ZHANG Chengwang, ZUO Songlin, HU He. Study of the preparation of shaped activated carbon for decoloring sugar solution from disused powered activated carbon[J]. Journal of Forestry Engineering, 2016, 1(4): 69-73.
28	EL-SHAFEY E I, ALI S N F, AL-BUSAFI S, et al. Preparation and characterization of surface functionalized activated carbons from date palm leaflets and application for methylene blue removal[J]. Journal of Environmental Chemical Engineering, 2016, 4(3): 2713-2724.
29	SHIN S, JANG J, YOON S H, et al. A study on the effect of heat treatment on functional groups of pitch based activated carbon fiber using FTIR[J]. Carbon, 1997, 35(12): 1739-1743.
30	冒爱琴, 王华, 谈玲华, 等. 活性炭表面官能团表征进展[J]. 应用化工, 2011, 40(7): 1266-1270.
	MAO Aiqin, WANG Hua, TAN Linghua, et al. Research progress in characterization of functional groups on activated carbon[J]. Applied Chemical Industry, 2011, 40(7): 1266-1270.
31	WANG N, JING B, WANG P, et al. Hygroscopicity and compositional evolution of atmospheric aerosols containing water-soluble carboxylic acid salts and ammonium sulfate: influence of ammonium depletion[J]. Environmental Science & Technology, 2019, 53(11): 6225-6234.
32	SHAFEEYAN M S, DAUD W M A W, HOUSHMAND A, et al. A review on surface modification of activated carbon for carbon dioxide adsorption[J]. Journal of Analytical and Applied Pyrolysis, 2010, 89(2): 143-151.
33	汪丰云, 彭云龙, 吕金安, 等. 焦糖色素与食品安全[J]. 化学教育, 2013, 34(7): 1-2, 5.
	WANG Fengyun, PENG Yunlong, Jin’an LYU, et al. Caramel and food safe[J]. Chinese Journal of Chemical Education, 2013, 34(7): 1-2, 5.
34	SZYMAŃSKI G S, KARPIŃSKI Z, BINIAK S, et al. The effect of the gradual thermal decomposition of surface oxygen species on the chemical and catalytic properties of oxidized activated carbon[J]. Carbon, 2002, 40(14): 2627-2639.
35	ÖRSI F. Kinetic studies on the thermal decomposition of glucose and fructose[J]. Journal of Thermal Analysis, 1973, 5(2/3): 329-335.

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